CN105895816B - A kind of inversion blue light quantum point membrane electro luminescent device and its manufacturing method - Google Patents
A kind of inversion blue light quantum point membrane electro luminescent device and its manufacturing method Download PDFInfo
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- CN105895816B CN105895816B CN201610213607.7A CN201610213607A CN105895816B CN 105895816 B CN105895816 B CN 105895816B CN 201610213607 A CN201610213607 A CN 201610213607A CN 105895816 B CN105895816 B CN 105895816B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/156—Hole transporting layers comprising a multilayered structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The present invention provides a kind of inversion blue light quantum point membrane electro luminescent devices, substrate, cathode, electron transfer layer, blue quantum dot light emitting layer, hole transmission layer and anode, hole transmission layer including stacking gradually include the first hole transmission layer, the second hole transmission layer and the third hole transmission layer that are laminated.The thickness of third hole transmission layer is 5nm~10nm.The HOMO energy levels of second hole transmission layer are more than the HOMO energy levels of the first hole transmission layer, so as to form steps potential barrier between blue light quantum point luminescent layer and anode, reach the Hole injection capacity for stepping up hole transmission layer, meet the requirement of the hole injection of blue light light quanta point membrane electro luminescent device.It is high that electroluminescent material device hole injection barrier of the invention is low, carrier is directly injected into mechanism height, luminous efficiency.The present invention also provides the methods for preparing as above inversion blue light quantum point membrane electro luminescent device.
Description
Technical field
The present invention relates to electroluminescent device technical field, particularly a kind of inversion blue light quantum point thin film electroluminescence device
Part and its manufacturing method.
Background technology
Semiconductor-quantum-point (QDs, the Quantum Dots) material of diameter between 2nm~10nm belongs to quasi-zero dimension
(quasi-zero-dimensional) nano material, it is also referred to as nanocrystalline.Since electronics, hole and exciton are in three dimensions
By quantum confinement on direction so that the discrete energy levels that the band structure of QDs is become to have molecular characterization by the continuous structure of block
Structure, when QDs grain sizes suitable or smaller with Wannier exciton Bohr radiuses, the locality of electronics and coherence's enhancing, exciton
The absorption coefficient of band increases, and exciton occurs and absorbs by force, hyperfluorescence can be emitted after being excited, and symmetrically emit light with narrow
The advantages that spectrum, wide and continuous absorption spectra.With QDs change in size, the effect of quantum effect enables it to gap width and changes therewith
Become, so as to send out the light of different colours.At present, it is mainly II-VI group nucleocapsid in the quantum dot of illumination field better performances
CdSe@ZnS (3nm~6nm) and ZnCdS@ZnS (8nm~15nm), although obstruction can be faced due to harmful heavy metal cadmium,
The QDs of cadmium is removed because of brightness and relatively inefficient, therefore is still weighed in the world by research of the CdSe@ZnS of nucleocapsid at present
Point.
Using QDs as sandwich structure electroluminescent diode (QLEDs, Quantum the Dot Light of luminescent layer
Emitting Diodes) also thus have the features such as high efficiency, rich in color, high stability, in addition QDs can solution add
Work feature, becoming QLEDs, next-generation flexible wearable is shown and lighting area enlivens very much and the research rich in application prospect
Hot spot.
The luminescent excitons of quantum dot can be formed by four kinds of modes, a) photoexcitation, take place mostly in high energy gap blue light,
It excites the green light of low band gap, feux rouges that it is made to shine after green luminescence again, very well should be obtained in LED backlight technology at present
With；B) carrier is directly injected into QDs from adjacent transport layer, is sent out in QLEDs when carrier injection barrier is less than 0.3eV
It is raw；C) exciton is formed in the adjacent luminescent layers of QDs, then reaching QDs by way of energy transmission makes it shine, in QLEDs
Occur when carrier injection barrier is higher than 0.3eV；D) electric field separates take place mostly in electrochemical field.
QLEDs devices of the prior art there are it is following the problem of：Prepared by the CdSe@ZnS materials of nucleocapsid
Main problem existing for QLED devices is highest molecule occupied orbital position (HOMO, the Highest of QDs materials in itself
Occupied Molecular Orbital) higher (>6.0eV), for particularly with green and blue QDs, HOMO energy levels
6.5eV is all higher than, and the HOMO energy levels of common hole mobile material are normally between 5.5eV~6.0eV, this is resulted in
The higher hole injection barrier of QLEDs devices so that carrier, which is directly injected into, to be formed the process of exciton and be restricted, while QDs
With wide, continuous absorption spectra causes it to be easy to absorb outside energy and form exciton, therefore, luminescent excitons in QLED
Form the collective effect being mainly directly injected by carrier with two kinds of mechanism of energy transmission.The raising that carrier is directly injected into is general
For will enhance QLEDs devices luminous efficiency；And energy transfer mechanism is due to generally from high gap material to low energy gap material
It carries out, therefore, for the blue and green light of high energy gap, the generation of energy transfer mechanism usually restricts carrying for its luminous efficiency
It is high.
Invention content
Based on this, it is necessary to provide that a kind of hole injection barrier is low, carrier is directly injected into the high electroluminescent cell of mechanism
Part and preparation method thereof can reach and improve hole injection barrier, improve the advantageous effect that carrier is directly injected into mechanism.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of inversion blue light quantum point membrane electro luminescent device, including substrate, cathode, the electron-transport stacked gradually
Layer, blue quantum dot light emitting layer, hole transmission layer and anode；Wherein, the hole transmission layer includes the first hole being laminated
Transport layer, the second hole transmission layer and third hole transmission layer, first hole transmission layer are in direct contact with the anode, institute
Third hole transmission layer is stated to be in direct contact with the blue quantum dot light emitting layer；The material of first hole transmission layer is first
The mass ratio of the mixture of hole layer material and the second hole layer material, first hole layer material and the second hole layer material
It is 1:2~3:2, the thickness of first hole transmission layer is 20nm~30nm；The material of second hole transmission layer is the
The mixture of one hole layer material and third hole layer material, the quality of first hole layer material and third hole layer material
Than being 1:4~1:2, the thickness of second hole transmission layer is 10nm~20nm；The material of the third hole transmission layer is
Third hole layer material, the thickness of the third hole transmission layer is 5nm~10nm；The HOMO energy of the third hole transmission layer
Grade is 6.04eV~6.8eV, and the HOMO energy levels of second hole transmission layer are 6.04eV~6.8eV, and first hole passes
The HOMO energy levels of defeated layer be 4.2eV~6.03eV, the third hole transmission layer, second hole transmission layer and described first
The HOMO energy levels of hole transmission layer are sequentially reduced.
Further, the material of the cathode is indium tin oxide, fluorine doped tin oxide, the zinc oxide for mixing aluminium and indium-doped oxygen
Change at least one of zinc.
Further, third hole layer material is selected from least one of mCP and BCPPA.
Further, second hole layer material be selected from N, N '-two (1- naphthalenes)-N, N '-diphenyl -1,1 '-biphenyl -
Bis- (9H- carbazole -9- bases) biphenyl of 4-4 '-diamines, 2,2 ' two (3- dimethyl benzenes aminobenzene) 1,1' biphenyl, 4,4'-, 8,8- bis-
(4- (9 hydrogen-carbazole -9- bases) phenyl) -8 hydrogen-indoles [3,2,1-de] acridine, (9 hydrogen-carbazole -9- the bases)-nitrogen of 3,5- bis- and nitrogen -
At least one of biphenyl ammonia.
Further, first hole layer material in molybdenum trioxide, tungstic acid, vanadium oxide and titanium cyanines copper extremely
Few one kind.
Further, the material of the anode is at least one of aluminium, silver, gold and platinum.
Further, the material of the blue quantum dot light emitting layer is CdSe ZnS core-shell structured quantum dots, wherein, table
Show cladding, " CdSe@ZnS " coats CdSe for ZnS；" ZnCdS@ZnS " coats ZnCdS for ZnS；The blue quantum dot light emitting layer
Thickness be 15nm~30nm.
The production method as described above for being inverted blue light quantum point membrane electro luminescent device, includes the following steps：Substrate
Upper to prepare the ITO conductive films that a layer thickness is 80nm~200nm, this ITO conductive film is cathode, and the material of the cathode is indium tin
At least one of oxide, fluorine doped tin oxide, the zinc oxide for mixing aluminium and indium-doped zinc oxide；Have to preparation the substrate of cathode according to
It is secondary to be respectively ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol, then carry out UV ozone processing 15min；In ITO conductions
On film electron transfer layer, blue quantum dot light emitting layer, electron-transport layer thickness 30nm~50nm are prepared with solution spin-coating method successively
In the range of, in the range of blue quantum dot light emitting layer thickness 15nm~30nm；It is made successively with vacuum vapour deposition on the electron transport layer
The third hole transmission layer that standby thickness is 5nm~10nm, second hole transmission layer of the thickness for 10nm~20nm, thickness 20nm
The first hole transmission layer of~30nm finally prepares the anode that thickness is 100nm~150nm.
Further, before by ITO conduction film preparations in substrate, first by substrate successively with detergent, acetone, ethyl alcohol
15min is respectively ultrasonically treated with isopropanol.
Further, method of the ITO conductions film preparation in substrate for vapor deposition, spraying plating, sputtering, electrochemistry evaporation sink
One kind in product or electrochemical means.
This electroluminescent device using the hole transmission layer of multi-layer doping, and meets and is sent out from anode to blue quantum dot
The HOMO energy levels of the hole transmission layer of photosphere are gradually incremented by successively, form the stepped gesture from anode to blue quantum dot light emitting layer
It builds.The first hole mobile material in the first hole transmission layer, the second hole transmission layer all containing high mobility, and first
Hole transmission layer, the second hole mobile material of hole mobile material of the second hole transmission layer, third hole mobile material
HOMO energy levels increase successively, and HOMO energy level progressive relationships layer by layer are formed, and make the interface between multilayer hole transmission layer with this
Potential barrier is further eliminated, and hole injection barrier is low, and hole injection barrier is gentler, and carrier is directly injected into mechanism height, with this
Reduce device drive voltage.It is to prevent that the hole mobile material to undope is used in the position for closing on blue quantum dot light emitting layer
First hole layer material of high mobility is in direct contact with blue quantum dot light emitting layer, is easy to luminescence queenching.Wherein second is empty
Cave layer material is 1 with the material doped quality of materials ratio of third cavitation layer:4~1:2, the first hole layer material and the second cavitation layer material
It is 1 to expect dopant material mass ratio:2~3:2.Since three layers of thickness of hole transport layer here can influence driving voltage, so needing
To determine every a layer thickness according to the property of material, mobility it is relatively low do it is thinner.Third hole transmission layer, the second sky
Cave transport layer, the first hole transmission layer thickness should respectively control between 5nm~10nm, 10nm~20nm, 20nm~30nm.
Description of the drawings
Fig. 1 is the structure diagram of the electroluminescent device of an embodiment；
Fig. 2 is the experimental comparison figure of the luminescent properties of the electroluminescent device of 1~embodiment of embodiment 3；
Fig. 3 is the structure diagram of the inversion green light quantum point membrane electro luminescent device of an embodiment.
Specific embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to accompanying drawings.It is provided in attached drawing
The preferred forms of the present invention.But the present invention can realize in many different forms, however it is not limited to be retouched herein
The embodiment stated.On the contrary, the purpose of providing these embodiments is that make to understand the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The normally understood meaning of technical staff is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein " and/or " including one or more
The arbitrary and all combination of relevant Listed Items.
As shown in Figure 1, the present invention inversions blue light quantum point membrane electro luminescent device including stack gradually substrate 1,
Cathode 2, electron transfer layer 3, blue quantum dot light emitting layer 4, hole transmission layer and anode 8.
Wherein, the material of substrate 1 can be the high glass of transmitance, convenient to splash on it since glass transmission performance is good
Penetrate or be deposited conductive film.
Electron transfer layer 3 selects the material of preferable electron mobility, can be to change zinc (ZnO), titanium dioxide (TiO2)
Deng.
The material of the cathode 2 can be from indium tin oxide (ITO), fluorine doped tin oxide (FTO), the zinc oxide for mixing aluminium
(AZO), it is selected in indium-doped zinc oxide (IZO).The thickness of cathode 2 can be 80nm~200nm.
The material of blue light quantum point luminescent layer 4 is blue light quantum point.Blue light quantum point for nucleocapsid CdSe@ZnS or
One kind in ZnCdS@ZnS.Wherein ,@represents cladding, and " CdSe@ZnS " coats CdSe, ZnCdS@ZnS, that is, ZnS claddings for ZnS
ZnCdS.In a preferred embodiment, using the CdSe@ZnS blue light quantum points of nucleocapsid more preferably, this nucleocapsid
Quantum dot, brightness is higher, and luminous efficiency is high, can directly buy on the market.The thickness of blue quantum dot light emitting layer by layer is 15
~30nm
Since the work function of the common transparent anode of electroluminescent device is less than 5eV, the HOMO energy with blue quantum dot
Grade (＞ 6.8eV) difference farther out, therefore causes hole injection barrier in electroluminescent device generally higher, needs high HOMO energy levels
Hole-injecting material help the injection in hole.When using just type device architecture is put, since blue quantum dot light emitting layer 4 needs
To be prepared using solwution method, limit hole injection of its lower floor, hole mobile material alternative.And using inverted structure
EL device structure when, hole mobile material can be after the completion of prepared by blue quantum dot light emitting layer 4 with vacuum evaporation
Prepared by mode class, therefore can have the selection of more high HOMO energy levels hole mobile materials and blue quantum dot light emitting layer energy level phase
Matching further, using the hole transmission layer of multi-layer doping, and meets from anode 8 to the sky of blue quantum dot light emitting layer 4
The HOMO energy levels of cave transport layer gradually increase, and form the steps potential barrier from anode 8 to blue quantum dot light emitting layer.
Specifically, hole transmission layer includes the first hole transmission layer 7, the second hole transmission layer 6 and the third hole that are laminated
Transport layer 5, the first hole transmission layer 7 are in direct contact with the anode 8, and third hole transmission layer 5 is sent out with the blue quantum dot
Photosphere 4 is in direct contact.
As shown in Fig. 2, the material of the first hole transmission layer 7 is the first hole layer material (HTL1) and the second hole layer material
(HTL2) mass ratio of mixture, the first hole layer material (HTL1) and the second hole layer material (HTL2) is 1:2~3:2,
The thickness of first hole transmission layer 7 is 20nm~30nm；The material of second hole transmission layer 6 is the first cavitation layer material
Expect the mixture of (HTL1) and third hole layer material (HTL3), first hole layer material (HTL1) and third cavitation layer material
The mass ratio for expecting (HTL3) is 1:4~1:2, the thickness of second hole transmission layer 6 is 10nm~20nm；The third hole
The material of transport layer 5 is third hole layer material (HTL3), and the thickness of the third hole transmission layer 5 is 5nm~10nm.
Electroluminescent device of the present invention is in the first hole transmission layer 7, the second hole transmission layer 6 all containing high mobility
First hole layer material (HTL1), and the second hole layer material in the first hole transmission layer 7, the second hole transmission layer 6
(HTL2), the HOMO energy levels of third hole layer material (HTL3) increase successively, and HOMO energy level progressive relationships layer by layer are formed with this,
And the interface potential barrier between multilayer hole transmission layer is made further to eliminate, hole injection barrier is gentler, and device is reduced with this
Driving voltage.It is to prevent high migration that the hole mobile material to undope is used in the position for closing on blue quantum dot light emitting layer 4
First hole layer material (HTL1) of rate is in direct contact with blue quantum dot light emitting layer 4, is easy to luminescence queenching.Traditional QLED
Only the hole transmission layer of individual layer or there is multilayered structure, be typically also to make identical thickness, due to three layers of hole here
Transmission layer thickness can influence driving voltage, so needing to determine every a layer thickness according to the property of material, mobility is relatively low
That does is thinner.Due to hole, the mobility at each position is not quite similar in hole transmission layer and hole balance layer, and hole passes
Defeated efficiency is low.The thickness of third hole transmission layer 5, the second hole transmission layer 6 and the first hole transmission layer 7 is sequentially increased, root
According to the variation of stair-stepping potential barrier and hole mobility, the thickness of each layer of hole transmission layer is rationally designed, improves the biography in hole
Defeated efficiency, and then improve the luminous efficiency of QLED.
The HOMO energy levels of the third hole transmission layer, second hole transmission layer and first hole transmission layer according to
Secondary reduction, the HOMO energy levels of the third hole transmission layer are 6.04eV~6.8eV, the HOMO energy of second hole transmission layer
Grade is 6.04eV~6.8eV, and the HOMO energy levels of first hole transmission layer are 4.2eV~6.03eV.
Third hole layer material (HTL3), second hole layer material (HTL2) and first hole layer material
(HTL1) HOMO energy levels are sequentially reduced, wherein the work function of the first hole material (HTL1) and the second hole material (HTL2)
The difference of HOMO energy levels is less than 0.7eV, and the difference of the work function of the first hole material (HTL1) and the work function of anode is less than
1.3eV forms the ladder of energy level.
The to undope is provided among the second hole transmission layer 5 and blue light quantum point luminescent layer 4 for being doped with material
Three hole transmission layers 5 can make on the basis of enough hole injections are ensured, can effectively reduce the leakage of electroluminescent device
Electric current improves luminous efficiency, and organizes the first hole layer material (HTL1) of high mobility and blue quantum dot light emitting layer 4
It is in direct contact, avoids causing luminescence queenching.
The material of first hole layer material (HTL1) can be from molybdenum trioxide (MoO3), tungstic acid (WO3), oxidation
Vanadium (V2O5) and the middle selection at least one of titanium cyanines copper (CuPc).
Second hole layer material (HTL2) can from N, N '-two (1- naphthalenes)-N, N '-diphenyl -1,1 '-biphenyl -
4-4 '-diamines (NPB), 2,2 ' two (3- dimethyl benzenes aminobenzene) 1,1' biphenyl (BTPD), 4,4'- bis- (9H- carbazole -9- bases) connection
Benzene (CBP), (4- (9 hydrogen-carbazole -9- bases) phenyl) -8 hydrogen-indoles [3,2,1-de] acridines (FPCC) of 8,8- bis- and 3,5- bis- (9
Hydrogen-carbazole -9- bases)-nitrogen, the middle selection at least one of nitrogen-biphenyl ammonia (DCDPA).
The material of third hole layer material (HTL3) can from 2- hydroxy-3-methyl -2- cyclopentene-1-ones (mCP),
It is selected in 6,6-bis (4- (9H-carbazol-9-yl) phenyl) -6H-pyrrolo [3,2,1-de] acridine (BCPPA)
It is at least one.
The material of the anode 8 can be selected from aluminium (Al), silver-colored (Ag), the gold high-work-function metals such as (Au) and platinum (Pt)
At least one, the metal of high work function can be conducive to reduce the barrier potential difference between anode 8 and blue light quantum point luminescent layer 4.
The present invention also provides a kind of methods for making electroluminescent device as described above, include the following steps：Substrate
Upper to prepare the ITO conductive films that a layer thickness is 80nm~200nm, this ITO conductive film is cathode, and the material of the cathode is indium tin
At least one of oxide (ITO), fluorine doped tin oxide (FTO), the zinc oxide (AZO) for mixing aluminium, indium-doped zinc oxide (IZO)；
The substrate for having cathode to preparation is respectively ultrasonically treated 15min, then carry out ultraviolet smelly with detergent, acetone, ethyl alcohol and isopropanol successively
Oxygen handles 15min；On ITO conductive films electron transfer layer, blue quantum dot light emitting layer, electronics are prepared with solution spin-coating method successively
It transmits in the range of layer thickness 30nm~50nm, in the range of 15~30nm of blue quantum dot light emitting layer thickness；On the electron transport layer
The third hole transmission layer that thickness is 5nm~10nm, the second sky that thickness is 10nm~20nm are sequentially prepared with vacuum vapour deposition
Cave transport layer, thickness are the first hole transmission layer of 20nm~30nm, finally prepare the anode that thickness is 100nm~150nm.
In some embodiments, before by ITO conduction film preparations in substrate, first by substrate successively with detergent,
Acetone, ethyl alcohol and isopropanol are respectively ultrasonically treated 15min.
Method of the ITO conductions film preparation in substrate is vapor deposition, spraying plating, sputtering, electrochemistry hydatogenesis or electrification
One kind in mode.
Embodiment 1
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is splashed in substrate 1
It penetrates a layer thickness and is the ITO conductive films of 150nm, then carry out UV-ozone and make 15min processing.Then it is being filled using solution spin-coating method
ZnO electron transfer layers 3 are prepared in full nitrogen and the extremely low glove box of water oxygen content, using the ZnO nano particle ethyl alcohol of 20mg/ml
Solution, rotating speed are 1500 revs/min (Resolutions per minute, rpm), and anneal 30min at 150 DEG C, and thickness is
40nm.Quantum dot light emitting layer is prepared later, using the blue CdSe ZnS quantum dots toluene solution of 20mg/ml, rotating speed
2000rpm, anneal at 150 DEG C 30min, thickness 20nm.It is 10 that device is transferred to pressure later-4High vacuum cavity under Pa
Interior, the BCPPA of vacuum evaporation 8nm is third hole transmission layer successively；15nm dopant materials mass ratio is 1:4 MoO3:BCPPA
Doped layer is the second hole transmission layer；25nm dopant materials mass ratio is 3:2 MoO3:CBP is the first hole transmission layer；Finally
The aluminium electrode of vacuum evaporation 100nm is as anode 8.
Embodiment 2
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is splashed in substrate 1
It penetrates a layer thickness and is the ITO conductive films of 150nm, then carry out UV-ozone and make 15min processing.Then it is being filled using solution spin-coating method
ZnO electron transfer layers 3 are prepared in full nitrogen and the extremely low glove box of water oxygen content, using the ZnO nano particle ethyl alcohol of 20mg/ml
Solution, rotating speed are 1500 revs/min (Resolutions per minute, rpm), and anneal 30min at 150 DEG C, and thickness is
40nm.Quantum dot light emitting layer is prepared later, using the blue CdSe ZnS quantum dots toluene solution of 20mg/ml, rotating speed
2000rpm, anneal at 150 DEG C 30min, thickness 20nm.It is 10 that device is transferred to pressure later-4High vacuum cavity under Pa
Interior, the BCPPA of vacuum evaporation 8nm is third hole transmission layer successively；20nm dopant materials mass ratio is 1:4 MoO3:BCPPA
Doped layer is the second hole transmission layer；30nm dopant materials mass ratio is 3:2 MoO3:CBP is the first hole transmission layer；Finally
The aluminium electrode of vacuum evaporation 100nm is as anode 8.
Embodiment 3
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is sputtered in substrate
A layer thickness is the ITO conductive films of 200nm, then carries out UV-ozone and make 15min processing.Then using solution spin-coating method full of
ZnO electron transfer layers 3 are prepared in nitrogen and the extremely low glove box of water oxygen content, it is molten using the ZnO nano particle ethyl alcohol of 20mg/ml
Liquid, rotating speed are 1500 revs/min (Resolutions per minute, rpm), and anneal 30min at 150 DEG C, and thickness is
40nm.Quantum dot light emitting layer is prepared later, using the blue CdSe ZnS quantum dots toluene solution of 20mg/ml, rotating speed
2000rpm, anneal at 150 DEG C 30min, thickness 20nm.It is 10 that device is transferred to pressure later-4High vacuum cavity under Pa
Interior, the BCPPA of vacuum evaporation 10nm is third hole transmission layer successively；20nm dopant materials mass ratio is 1:4 MoO3:
BCPPA doped layers are the second hole transmission layer；30nm dopant materials mass ratio is 3:2 MoO3:CBP is the first hole transport
Layer；The aluminium electrode of last vacuum evaporation 100nm is as anode 8.
Embodiment 4
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is used in substrate 1
Electrochemical means prepare a layer thickness and are the FTO conductive films of 150nm, then carry out UV-ozone and make 15min processing.Then using molten
Liquid spin-coating method prepares ZnO electron transfer layers 3 in full of nitrogen and the extremely low glove box of water oxygen content, using the ZnO of 20mg/ml
Nano particle ethanol solution, rotating speed are 1500 revs/min (Resolutions per minute, rpm), are annealed at 150 DEG C
30min, thickness 40nm.Quantum dot light emitting layer is prepared later, it is molten using the blue CdSe ZnS quantum dots toluene of 20mg/ml
Liquid, rotating speed 2000rpm, anneal at 150 DEG C 30min, thickness 20nm.It is 10 that device is transferred to pressure later-4Height under Pa
In vacuum cavity, the mCP of vacuum evaporation 5nm is third hole transmission layer successively；10nm dopant materials mass ratio is 1:4 WO3:
MCP doped layers are the second hole transmission layer；20nm dopant materials mass ratio is 1:2 WO3:NPB is the first hole transmission layer；Most
The silver electrode of vacuum evaporation 100nm is as anode 8 afterwards.
Embodiment 5
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is steamed in substrate 1
It plates a layer thickness and is the ITO conductive films of 80nm, then carry out UV-ozone and make 15min processing.Then it is being filled using solution spin-coating method
ZnO electron transfer layers 3 are prepared in full nitrogen and the extremely low glove box of water oxygen content, using the ZnO nano particle ethyl alcohol of 20mg/ml
Solution, rotating speed are 1500 revs/min (Resolutions per minute, rpm), and anneal 30min at 150 DEG C, and thickness is
30nm.Quantum dot light emitting layer is prepared later, using the blue CdSe ZnS quantum dots toluene solution of 20mg/ml, rotating speed
2000rpm, anneal at 150 DEG C 30min, thickness 15nm.It is 10 that device is transferred to pressure later-4High vacuum cavity under Pa
Interior, the mCP of vacuum evaporation 10nm is third hole transmission layer successively；15nm dopant materials mass ratio is 1:2 V2O5:MCP is adulterated
Layer is the second hole transmission layer；30nm dopant materials mass ratio is 3:2 V2O5:FPCC is the first hole transmission layer；Last vacuum
The platinum electrode of 100nm is deposited as anode 8.
Embodiment 6
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is sprayed in substrate 1
It plates a layer thickness and is the IZO conductive films of 200nm, then carry out UV-ozone and make 15min processing.Then it is being filled using solution spin-coating method
TiO is prepared in full nitrogen and the extremely low glove box of water oxygen content2Electron transfer layer 3, using the TiO2 nano particle second of 20mg/ml
Alcoholic solution, rotating speed are 1500 revs/min (Resolutions per minute, rpm), and anneal 30min at 150 DEG C, thickness
For 50nm.Quantum dot light emitting layer is prepared later, using the blue CdSe ZnS quantum dots toluene solution of 20mg/ml, rotating speed
2000rpm, anneal at 150 DEG C 30min, thickness 30nm.It is 10 that device is transferred to pressure later-4High vacuum cavity under Pa
Interior, the mCP of vacuum evaporation 10nm is third hole transmission layer successively；20nm dopant materials mass ratio is 1:3 CuPc:MCP mixes
Diamicton is the second hole transmission layer；25nm dopant materials mass ratio is 1:1 CuPc:DCDPA is the first hole transmission layer；Finally
The silver electrode of vacuum evaporation 125nm is as anode 8.
Embodiment 7
Substrate 1 is respectively first ultrasonically treated 15min with detergent, acetone, ethyl alcohol and isopropanol successively.Then it is used in substrate 1
One layer of electrochemistry hydatogenesis prepares thickness and is the AZO conductive films of 120nm, then carry out UV-ozone and make 15min processing.Then it adopts
ZnO electron transfer layers 3 are prepared in full of nitrogen and the extremely low glove box of water oxygen content with solution spin-coating method, using 20mg/ml
ZnO nano particle ethanol solution, rotating speed be 1500 revs/min (Resolutions per minute, rpm), at 150 DEG C
Anneal 30min, thickness 35nm.Quantum dot light emitting layer is prepared later, using the ZnCdS ZnS blue quantum dot first of 20mg/ml
Benzole soln, rotating speed 2000rpm, anneal at 150 DEG C 30min, thickness 20nm.It is 10 that device is transferred to pressure later-4Under Pa
High vacuum cavity in, successively the mCP of vacuum evaporation 10nm be third hole transmission layer；20nm dopant materials mass ratio is 1:2
CuPc:MCP doped layers are the second hole transmission layer；30nm dopant materials mass ratio is 3:2 CuPc:BTPD is the first hole
Transport layer；The gold electrode of last vacuum evaporation 150nm is as anode 8.
Embodiment 8
Fig. 3 is to be using structure：ITO/ZnO/Blue-QDs/NPB/MoO3The comparative device and reality of the traditional structure of/Al
Apply the voltage of 1~embodiment of example 3 and brightness relationship comparison diagram, it can be seen that under same voltage, electroluminescent cell of the present invention
The effect of part is more excellent than traditional electroluminescent device.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. it is a kind of inversion blue light quantum point membrane electro luminescent device, which is characterized in that including stack gradually substrate, cathode,
Electron transfer layer, blue quantum dot light emitting layer, hole transmission layer and anode；Wherein,
The hole transmission layer includes the first hole transmission layer, the second hole transmission layer and the third hole transmission layer that are laminated, institute
It states the first hole transmission layer to be in direct contact with the anode, the third hole transmission layer and the blue quantum dot light emitting layer are straight
Contact；
Mixture of the material of first hole transmission layer for the first hole layer material and the second hole layer material, described first
The mass ratio of hole layer material and the second hole layer material is 1:2~3:2, the thickness of first hole transmission layer for 20~
30nm；
Mixture of the material of second hole transmission layer for the first hole layer material and third hole layer material, described first
The mass ratio of hole layer material and third hole layer material is 1:4~1:2, the thickness of second hole transmission layer for 10~
20nm；
The material of the third hole transmission layer is third hole layer material, the thickness of the third hole transmission layer for 5~
10nm；
The HOMO energy levels of the third hole transmission layer be 6.04eV~6.8eV, the HOMO energy levels of second hole transmission layer
For 6.04eV~6.8eV, the HOMO energy levels of first hole transmission layer are 4.2eV~6.03eV, the third hole transport
The HOMO energy levels of layer, second hole transmission layer and first hole transmission layer are sequentially reduced, the third hole transport
The thickness of layer, second hole transmission layer and first hole transmission layer is sequentially increased.
2. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that the cathode
Material is at least one of indium tin oxide, fluorine doped tin oxide, the zinc oxide for mixing aluminium and indium-doped zinc oxide.
3. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that the third is empty
Cave layer material is selected from least one of mCP and BCPPA.
4. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that described second is empty
Cave layer material is selected from N, N '-two (1- naphthalenes)-N, N '-diphenyl -1,1 '-biphenyl -4-4 '-diamines, 2,2 ' two (3- dimethyl benzenes
Aminobenzene) 1,1' biphenyl, bis- (9H- carbazole -9- bases) biphenyl of 4,4'-, 8,8- bis- (4- (9 hydrogen-carbazole -9- bases) phenyl) -8 hydrogen -
Indoles [3,2,1-de] acridine, 3,5- bis- (9 hydrogen-carbazole -9- bases) at least one of-nitrogen and nitrogen-biphenyl ammonia.
5. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that described first is empty
Cave layer material is selected from least one of molybdenum trioxide, tungstic acid, vanadium oxide and titanium cyanines copper.
6. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that the anode
Material is at least one of aluminium, silver, gold and platinum.
7. inversion blue light quantum point membrane electro luminescent device according to claim 1, which is characterized in that the amount of blue
The material of son point luminescent layer is one kind in CdSe@ZnS core-shell structured quantum dots or ZnCdS@ZnS, wherein,
@represents cladding, and " CdSe@ZnS " coats CdSe for ZnS；" ZnCdS@ZnS " coats ZnCdS for ZnS；
The thickness of the blue quantum dot light emitting layer is 15nm~30nm.
It is 8. special such as the production method that claim 1~7 any one of them is inverted blue light quantum point membrane electro luminescent device
Sign is, includes the following steps：
In substrate prepare a layer thickness be 80nm~200nm ITO conductive films, this ITO conductive film be cathode, the material of the cathode
Expect at least one of indium tin oxide, fluorine doped tin oxide, the zinc oxide for mixing aluminium and indium-doped zinc oxide；
The substrate for having cathode to preparation is respectively ultrasonically treated 15min, then carry out purple with detergent, acetone, ethyl alcohol and isopropanol successively
Outer ozone treatment 15min；
On ITO conductive films electron transfer layer, blue quantum dot light emitting layer, electron-transport thickness are prepared with solution spin-coating method successively
It spends in the range of 30~50nm, in the range of 15~30nm of blue quantum dot light emitting layer thickness；
On the electron transport layer the third hole transmission layer that thickness is 5~10nm, thickness 10 are sequentially prepared with vacuum vapour deposition
The second hole transmission layer of~20nm, thickness are the first hole transmission layer of 20~30nm, finally prepare thickness for 100~
The anode of 150nm.
9. the production method according to claim 8 for being inverted blue light quantum point membrane electro luminescent device, which is characterized in that
Before by ITO conduction film preparations in substrate, first by substrate successively at detergent, acetone, ethyl alcohol and each ultrasound of isopropanol
Manage 15min.
10. the production method according to claim 8 for being inverted blue light quantum point membrane electro luminescent device, feature exist
In method of the ITO conductions film preparation in substrate is vapor deposition, spraying plating, sputtering, electrochemistry hydatogenesis or electrochemical means
In one kind.
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